Electronic Structure, Optical and Magnetic Properties of Oxygen-Deficient Gray TiO_2–δ(B)

The gray-colored oxygen-deficient TiO2–δ(B) nanobelts have been synthesized through a combination of the hydrothermal method followed by an ion exchange process and vacuum annealing. Electron paramagnetic resonance reveals an existence of F-centers in the form of electron-trapped oxygen vacancies within the anionic sublattice of the gray bronze TiO2 that induces its colouration. The diffuse reflectance spectroscopy showed that the formation of oxygen vacancies into TiO2(B) significantly increases its absorption intensity in both visible and near infrared ranges. The band gap of TiO2(B) with anionic defects is equal to 3.03 eV (against 3.24 eV for white TiO2(B) treated in air). Room temperature ferromagnetism associated with the defects was detected in gray TiO2–δ(B), thus indicating it belongs it to the class of dilute magnetic oxide semiconductors. It was found that in the low-temperature range (4 K), the magnetic properties of vacuum annealed TiO2(B) do not differ from those for TiO2(B) treated in air. We hope that the findings are defined here make a contribution to further progress in fabrication and manufacturing of defective TiO2-based nanomaterials for catalysis, magnetic applications, batteries, etc

Zr4+/F– co-doped TiO2(anatase) as high performance anode material for lithium-ion battery

Zr4+ and F– co-doped TiO2 with the formula of Ti0.97Zr0.03O1.98F0.02 was facilely synthesized by a sol-gel template route. The crystal structure, morphology, composition, surface area, and conductivity were characterized by Raman spectroscopy, energy-dispersive X-ray analysis, scanning electron microscopy, Brunauer−Emmett−Teller measurements, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. The results demonstrate that Zr4+ and F– homogeneously incorporated into TiO2, forming solid solution with an anatase structure. Ti0.97Zr0.03O1.98F0.02 shows outstanding electrochemical properties as Li-ion battery anode in comparison with Ti0.97Zr0.03O2. In particular, upon 35-fold cycling at 1C-rate Zr4+/F– co-doped TiO2 delivers a reversible capacity of 163 mAh g–1, whereas Zr4+-doped TiO2 gives only 34 mA h g–1. Additionally, Zr4+/F– co-doped TiO2 retains a capacity of 138 mA h g–1 during cycling even at 10 C. The enhance performance originates from improved conductivity of Zr4+/F– co-doped TiO2 material through generation of Ti3+ (serving as electron donors) into the crystal lattice and, possibly, due to F-doping blocked the anode surface from attack of HF formed as electrolyte decomposition product. Keywords: Li-ion batteries, TiO2(anatase), Anode, Co-doping, Sol-gel template, Process, Electrochemical performanc

Moss-like Hierarchical Architecture Self-Assembled by Ultrathin Na2Ti3O7 Nanotubes: Synthesis, Electrical Conductivity, and Electrochemical Performance in Sodium-Ion Batteries

Nanocrystalline layer-structured monoclinic Na2Ti3O7 is currently under consideration for usage in solid state electrolyte applications or electrochemical devices, including sodium-ion batteries, fuel cells, and sensors. Herein, a facile one-pot hydrothermal synthetic procedure is developed to prepare self-assembled moss-like hierarchical porous structure constructed by ultrathin Na2Ti3O7 nanotubes with an outer diameter of 6–9 nm, a wall thickness of 2–3 nm, and a length of several hundred nanometers. The phase and chemical transformations, optoelectronic, conductive, and electrochemical properties of as-prepared hierarchically-organized Na2Ti3O7 nanotubes have been studied. It is established that the obtained substance possesses an electrical conductivity of 3.34 × 10−4 S/cm at room temperature allowing faster motion of charge carriers. Besides, the unique hierarchical Na2Ti3O7 architecture exhibits promising cycling and rate performance as an anode material for sodium-ion batteries. In particular, after 50 charge/discharge cycles at the current loads of 50, 150, 350, and 800 mA/g, the reversible capacities of about 145, 120, 100, and 80 mA∙h/g, respectively, were achieved. Upon prolonged cycling at 350 mA/g, the capacity of approximately 95 mA∙h/g at the 200th cycle was observed with a Coulombic efficiency of almost 100% showing the retention as high as 95.0% initial storage. At last, it is found that residual water in the un-annealed nanotubular Na2Ti3O7 affects its electrochemical properties

Data from: Effect of Hf-doping on electrochemical performance of anatase TiO2 as an anode material for lithium storage

Hafnium-doped titania (Hf/Ti = 0.01; 0.03; 0.05) had been facilely synthesized via a template sol-gel method on carbon fiber. Physicochemical properties of the as-synthesized materials were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetry analysis, and Brunauer−Emmett−Teller measurements. It was confirmed that Hf4+ substitute in the Ti4+ sites, forming Ti1–xHfxO2 (x = 0.01; 0.03; 0.05) solid solutions with an anatase crystal structure. The Ti1–xHfxO2 materials are hollow microtubes (length of 10–100 μm, outer diameter of 1–5 μm) composed of nanoparticles (average size of 15–20 nm) with surface area of 80–90 m2 g–1 and pore volume of 0.294–0.372 cm3 g–1. The effect of hafnium ions incorporation on electrochemical behavior of anatase TiO2 as Li-ion battery anode was investigated by galvanostatic charge/discharge and electrochemical impedance spectroscopy. It was established that Ti0.95Hf0.05O2 shows significantly higher reversibility (154.2 mAh g–1) after 35-fold cycling at C/10 rate in comparison with undoped titania (55.9 mAh g–1). The better performance offered by Hf4+ substitution of the Ti4+ into anatase TiO2 mainly results from more open crystal structure, which has been achieved via the difference in ionic radius values of Ti4+ (0.604 Å) and Hf4+ (0.71 Å). The obtained results are in a strong accordance with ones for anatase TiO2 doped via Zr4+ (0.72 Å) published earlier. Furthermore, improved electrical conductivity of Hf-doped anatase TiO2 materials due to charge redistribution in the lattice and enhanced interfacial lithium storage due to increased surface area directly depending on Hf/Ti atomic ratio have beneficial effect on electrochemical properties

Enhancing Lithium and Sodium Storage Properties of TiO2(B) Nanobelts by Doping with Nickel and Zinc

Nickel- and zinc-doped TiO2(B) nanobelts were synthesized using a hydrothermal technique. It was found that the incorporation of 5 at.% Ni into bronze TiO2 expanded the unit cell by 4%. Furthermore, Ni dopant induced the 3d energy levels within TiO2(B) band structure and oxygen defects, narrowing the band gap from 3.28 eV (undoped) to 2.70 eV. Oppositely, Zn entered restrictedly into TiO2(B), but nonetheless, improves its electronic properties (Eg is narrowed to 3.21 eV). The conductivity of nickel- (2.24 × 10−8 S·cm−1) and zinc-containing (3.29 × 10−9 S·cm−1) TiO2(B) exceeds that of unmodified TiO2(B) (1.05 × 10−10 S·cm−1). When tested for electrochemical storage, nickel-doped mesoporous TiO2(B) nanobelts exhibited improved electrochemical performance. For lithium batteries, a reversible capacity of 173 mAh·g−1 was reached after 100 cycles at the current load of 50 mA·g−1, whereas, for unmodified and Zn-doped samples, around 140 and 151 mAh·g−1 was obtained. Moreover, Ni doping enhanced the rate capability of TiO2(B) nanobelts (104 mAh·g−1 at a current density of 1.8 A·g−1). In terms of sodium storage, nickel-doped TiO2(B) nanobelts exhibited improved cycling with a stabilized reversible capacity of 97 mAh·g−1 over 50 cycles at the current load of 35 mA·g−1

Supplementary Figures and Tables from Effect of Hf-doping on electrochemical performance of anatase TiO₂ as an anode material for lithium storage

Figure S1: SEM image and elemental mapping of Ti, O, and Hf for Ti_0.95Hf_0.05O₂; Figure S2: XPS high-resolution spectra of (a) Ti 2p, (b) O 1s, (c) Hf 4f, and (d) C 1s regions for Ti_0.95Hf_0.05O₂ sample; Figure S3: Dependence of Z^' on ω^–1/2 at low frequencies; Table S1: Binding energy and atomic concentration of elements in Ti_0.95Hf_0.05O₂ sample; Table S2: Dependence of <i>E</i>_g(1), <i>B</i>_1<i>g</i>(1), and <i>E</i>_<i>g</i>(3) peaks positions on Hf/Ti atomic rati